Water-insoluble monoazo dye



Patented Oct. 11, 1938 UNITED STAT-ES WATER-INSOLUBLE 'MONOAZO D YE Miles Augustinus Dahlen, Wilmington, Del., and Martin Edwin Friedrich, Carneys Point, N. J., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application December 1'7, 1935, Serial. No. 54,851

2 Claims. (01250 -204;

This invention relates to new compositions of matter and to dyeing. More particularly the invention relates to new compositions of matter including azo dyes, and to processes of employing them, particularly in printing processes. The invention will be described with reference to particular examples which are illustrative but not limitative thereof. 7

The azo dyes are a well-defined group containing the chromophor -N=N. The chromogen of azo dyestuffs comprises two aryl radicals with the chromophor between them. The mono azo dyes are generally prepared by joining two components of which the first, an amine, is called the azo component, and the second, usually a phenol, an amine, or an active methylene com-.

pound, is called the coupling component. In coupling the components, the azo component is diazotized, and is reacted with the second component, usually in solution.

The azo dyes of the prior art are applied by one of several processes that have been devised to take advantage of the nature of particular dyes: (a) The dyestuff is dissolved or dispersed in a suitable liquid medium and the material to be dyed is dipped therein. Satisfactory results are obtained by this method only if the completed dyestuff is substantive to the material which is to be dyed. (b) A substantive coupling component, or a substantive azo component, is directly affixed to the material, and the diazotiz ed component or the coupling component,-respectively, is coupled thereto, completing the dye on the material. (0) An azo component is diazotized and coupled to a compound with which it forms a new compound stable in alkaline or neutral medium, and is mixed with the coupling component and with the other ingredients of a basic or neutral printing paste, or solution. The material to be dyed is impregnated with the paste, or with the solution, by printing or in any other satisfactory manner and the dye is formed on the material by reaction with an acid, whereby it is freed and enabled to react with the coupling component. This invention relates to new compositions of matter to be applied by the third of these methods, and to processes of applying them.

It is an object of the invention to make, use, and vend new dyestufis: to make them by processes which are economically and technically satisfactory and to apply them to dye-susceptible materials by methods and in compositions best suited to the attaining of optimum results. Other objects of the invention will be in part apparent and in part more fully hereinafter set forth.

OH (JOHN (311$ in which X is one of the group consistingv of hydrogen, halogen, and alkyl. Other objects of the invention are attained by preparing the said mixtures as dry powders, as paste, or in solution, 120 and by incorporating them in printing pastes and other dyeing compositions. The objects of the invention are accomplished, in one specific modification, by impregnating .a fabric or a fibrous naterial with abasic or neutral paste containing a mixture of thestabilized azo component and the coupling component and exposing the impregnated material, preferably at elevated temperature, to the action of a preferably mild acid. Still other objects of the invention are accomplished by the processes of applying the new compositions of matter more fully hereinafter set forth. Another object of the invention is accomplished by dyeing a material with a dye having the formula:

on, X

(Y)... 011 COHN in which Y is one of a group consisting of hydrogen and an n-auxochrome, m is an integer less than 6 andX is one of the group consisting of hydrogen, halogen, and alkyl. Another object of pounds which we have discovered to be useful as coupling components for azo dyes.

In the practice of the invention the azo component is stabilized against reaction in alkaline or neutral medium with a coupling component either by forming the nitrosamine or a diazoimino compound thereof. The stabilized azo component will then be mixed in the form of dry powder, a paste, or a solution with the alkaline or neutral mass containing the coupling component. The details of the processes of practicing the invention will differ somewhat according to the state of the ingredients but the general method is to impregnate the colorable material with the so-formed mixture, and to act upon it with enough acid to regenerate the azo component and permit it to act upon the coupling component.

In the form of the invention which involves the dyeing of a cloth by the so-called process of printing, the azo component, diazotized and stabilized as hereinabove described, is mixed in a basic paste with the coupling component, the

paste is applied to an etched or printing roller' which impregnates the fabric by contact, the fabric is placed in a closed container, and is subjected for a few seconds, at elevated temperature and usually in the presence of water vapor, to the action. of the fumes of an acid which-neutralizesthe basicity of the paste, breaks up the-stabilized complex, and frees the azo component for reaction with the coupling component.

The azo components may advantageously include as substituents in thearyl nucleus from one to five of the group alkyl, alkoxy, halogen, aryloxy, aralkyl, aralkoxy, aryl, hydroaryloxy, and trifluoro-alkyl, which are called n-auxochromes, but generally speaking satisfactory results are obtained by the use ofazo components having from one to three of these substituents. Illustrative of the general utility as azo components of the primary arylamines are the following:

Ortho-chloro-aniline 2 S-dichloro-aniline 4-chloro-2-amino-phenetol Ortho-anisidine 4-chl0ro2 E-dimethyl-aniline 4-benzoyl-amino-2:5-dimethoxy-aniline 5-nitro-2amino-anisole I-methoxy-Z-naphthylamine 4-chloro-2-amino-diphenyl ether Meta-amino-benzo-trifluoride Ortho-amino-azo-toluene 4 :4 -diamino-diphenylamine 3-amino-carbazole. Y

0 ONE Other methods of coloring dye-susceptible materials with the new dyes include the following: Textile fibers are impregnated with our new coupling components and are developed in diazoe salt solutions prepared from the diazotized arylamines hereinabove described; textile fibers may be voverprinted with the paste containing the diazo-salt' of an arylamine, producing the color according to the pattern of the printing roller; the new arylamides may be mixed with the diazotates (nitrosamines) derived from the diazotized arylamines useful as azo components, dyesusceptible materialsmay befimpregnated there with and subjected to the action of weak acids.

Any of the usual stabilizing agents may be used in the preparation of water-soluble diazoimino compounds. The following are exemplary, but not limitative, of the class:

Sarcosin l-methyl-amino-ethane-2-sulfonicacid Proline Nipecotinic-acid Benzylene-imine-para-sulfonic-acid 1-naphthylamine-2 4 8-trisulfonic-acid 2-ethyl-amino-4-sulfo-benzoic-acid Examples of other derivatives of diazotized arylamines which are inactive toward coupling components under alkaline conditions, but which revert to the diazo form when reacted upon by acids, are for instance the so-called diazo-sulfonates, compounds which have the type formula ArylN=N-SO3Na.

The following examples, in which parts are by Weight, are designed to illustrate but not to limit the various features of the invention:

EXAMPLE I A solution of the 2:3-hydroxy-naphthoyl derivative of 2:4:5-trimethyl-aniline was prepared as follows: 8 parts of the 2:4:5-trimethyl-anilide of 2:3-hydroXy-naphthoic-acid were pasted up with 10 parts of ethyl alcohol, 10 parts of caustic sodaof; 35 B. were admixed, and after the arylamide had dissolved completely, sufficient Water was added to bring the total volume up to 1600- parts.

12 parts of ortho-dianisidine were dissolved in a mixture of 22 parts of sulfuric-acid of 66 B. strength and 60 parts of hot water, the solution was poured onto an excess of ice, and the tetrazotization carried out with a solution of 7 parts of sodium nitrite dissolved in 15 parts of water. 7

40 parts of cotton piece goods, well-boiled and dried,.were impregnated with the solution of the naphthoyl derivative, the impregnated cloth was wrung out and, without drying, developed in the tetrazo solution. Just before coupling, the tetrazo solution was made slightly alkaline with sodium-bicarbonate.

The dyed cloth was rinsed, soaped at the boil, rinsed, and dried, giving a bright blue dyeing, having good fastness to light and excellent fastness to chlorine. It is represented by the formula:

0cm ooze CH3 -on (3H3 CH3 CONHQCH3 3113 CH3 EXAMPLE II The cloth was impregnated as in Example I and was developed in a solution prepared as follows:

14.1 parts of 4-chloro-2-amino-toluene were dissolved in 25.0 parts of hydrochloric-acid (37%) and 40 parts of water, the solution was cooled to 05 C., by means of external cooling, and a solution of 7 parts of sodium-nitrite dissolved in par-ts of'water was added. The temperature was held at 0-5 C. by the addition of about 50-parts of ice until diazotization was comuse plete, :the solution of the tdiazo salt was filtered,

and its mineral acidity was neutralized by the addition .of sodiumeace aW- The dyed cloth was rinsed, soaped at the boil, rinsed, and dried, giving a bri ht red 01011, having good fastness properties. sented by the formula:

ONE on;

EXAMPLE A printing paste ,wasprepared according .to the formula 1.8 parts of the '2:3-ihyd;r0xy-naph-thoyl derivative of 2 4 -trimethyl-aniline 2.2 parts of a diazoimino compound prepared from diazotized 4- c1 11oro-2-amino-aniso1e and piperidine-alpha-carboxylic acid 3.0 parts of caustic soda (40 Be.) 65.0 parts of starch tragaeanth thickener 28.0 parts of water Clattongpi c go ds were prin ed --w t th p rinting paste, then developed by subjecting to the action of ive s eam cont ining the v por of acetic-acid. gthis' ma nergthepa'ttern was developed as a red dyeing, having very good fast- Cotton goods were impregnated with the 2:4:526 tetramethyl anilide of 2:3 hydroxynaphthoic-acid, by the method describedin Example I. The padded goods were developed in a diazo solution prepared as in Example II.

The dyed cloth was rinsed, soaped at the boil, rinsed, and dried. A bright red dyeing was obtained. The dye has the probable formula:

CONH OH:

H: CH;

The .dye is repre-- 1 Exempt. v

A p nt g paste was p epare c o d n o the following formula: I

V 3.2 parts of the 2:3-hydroxyenaphthoy1deriva- 1*.

tive of 2:4:5:6-tetramethyl-ani1ine '2.7 parts of "the dried anti-diazotate obtained from 2: 5-dichloro-aniline 3.0 parts of caustic soda l0 B.) 65.0 parts of starch tragacanth thickener 26.1 parts of water Cotton piece goods were printed with the printing paste, and developed in the usual manner in an acid ager. There was obtained an orange printing from a dye of the probableformula:

EXAMPLE Cottonlpiecegoods were printed with a printing paste of the formula ,given in Example III, except that the :6t-:brom o.-'214:,5-trimethyhanilide of 2:3- I

hydroxyenaphthoicacid was usedas the coupling component. ion {treatment with live steam con taining the rvapors .of acetic-acid, the pattern was developed in red. The new color is represented by the formula:

OOH:

OH CH:

C ONH- CH2 EXAMPLE V11 Cotton goods were impregnated with the pentamethyl-anilide of 2:3-hydroxy-naphthoic-aci-d by the method described in Example I. The padded goods were developed in a diazo solution prepared as in Example II. The dyed cloth was rinsed, soaped at the boil, rinsed, and dried. A bright red dyeing was obtained, the dye having the probable formula:

OH CH: CH:

C ONH OH:

OH: CH3

The following examples describe a variety of other colors WhlCh have been successfully pro- As many apparently widely d1terent-emb0d1- duced by the use of other combinations of couments of this invention may be made without pling components and d1azot1zed arylammes. departing from the spirit-and scope thereof,'1t

1' 5 Exlggple Diazo component Coupung colrigggrggnog 12.3 hydroxy' I I Shade i 9 p-nitro-o-anisidine 2:4:5-trimetl1yl-aniline Scarlet. p-chlor-o-nitro-aniline do Red. 2:5dichlor-aniline o Scarlet to orange. 4:4-diamino-3:3-dimethoxydiphenyl 0..-. e blue. 10 4-benzoyl-amino-2:5;diethoxy-anilinedo Reddish blue. 4-annno-4-eth0xy-d1phenyl-amine do Blue. 5-n1tro-2-an11no-anisoledo Bordeaux. p-amino-dipl1e11yl-ether do Scarlet. p-nitro-o-anisidine 2-4z5-trimethyl Pink to scarlet. p-chlor-o-nitro-anilin d Scarlet. XVIII 2:5-dichlor-aniline do Orange. XIX 4:4-diamino-3:3-dimethoxy-diphenyl do Greeuish blue. 15

XX 4-benzoyl-amino-2:5-diethoxy-aniline do Reddish blue. XXI- -amino-4-ethoxy-diphenyl-amine do Gray blue. XXII 5-nitro2-amino-anisole "do Bluish red.

XXIIlI: p-amino-diphenyl-ether do Orange red.

The invention is applicable to the dyeing of is to be understood that we do not limit ourselves 20 cotton, regenerated cellulose, cellulose esters and to the specific embodiments thereof except as ethers and, with somewhat less satisfactory redefined in the appended claims. sults, to the dyeing of wool, silk, and leather. We claim:

The new products are also valuable as insoluble 1. A dyestuff represented by the formula: color pigments when produced apart from the OCHa 25 fiber. y Among the other new arylamides of 2:3-hy- N=N droxy-naphthoic-acid, suitable for the preparation of the new colors, the following may be 01 mentioned: 30 Arylamzde of 2.3 hydroxy naphthow aczd CH3 6-chloro-2 4 S-trimethyl-anilide 6-fiuoro-2 4 5-trimethy1-anilide 3 3-chloro-214:5-trimethyl-anilide 2. A fibrous material dyed with the color of 35 3-bromo-2:4z5-trimethyl-anilide claim 1. 6-ethyl-224:5-trimethyl-anilide MILES AUGUSTINUS DAHLEN. 3-ethyl-2z4:fi-trimethyl-anilide MARTIN EDWIN FRIEDRICH. 

